J Therm Anal Calorim (2011) 103:1017–1026

DOI 10.1007/s10973-010-1022-3

Non-isothermal crystallization kinetics and thermal stability

of the in situ reinforcing composite films based on thermotropic
liquid crystalline polymer and polypropylene
Sayant Saengsuwan • Pongsathorn Tongkasee •

Taweesak Sudyoadsuk • Vinich Promarak •

Tinnagon Keawin • Siriporn Jungsuttiwong

Received: 1 June 2010 / Accepted: 24 August 2010 / Published online: 10 September 2010
Ó Akadémiai Kiadó, Budapest, Hungary 2010

Abstract The non-isothermal crystallization kinetics and Abbreviations

thermal stability of the in situ reinforcing composite thin DSC Differential scanning calorimetry
film, comprising of 10 wt% of thermotropic liquid crys- DTG Differential thermogravimetry
talline polymer (TLCP, Rodrun LC5000) and polypropyl- HBA p-Hydroxy benzoic acid
ene (PP), prepared by a two-step method were investigated PBT Poly(butylene terephthalate)
using differential scanning calorimetry (DSC) and ther- PET Polyethylene terephthalate
mogravimetry (TG), respectively. The DSC results PP Polypropylene
revealed that Mo method was suitable for the crystalliza- TG Thermogravimetric analyzer
tion behavior description of both neat PP and TLCP Thermotropic liquid crystalline polymer
10 wt%TLCP/PP films. The in situ formation of TLCP TP Thermoplastic
fibrils in the PP matrix led to reduction in both values of DE Activation energy
half-time of crystallization (t1/2) and the kinetic parameter k The rate constant of Avrami equation
of Mo equation F(T), resulting in a significant increase in kc The kinetic crystallization rate constant
the crystallization rate of PP phase. The remarkable lower K(T) The kinetic parameter of Ozawa equation
in crystallization activation energy of the composite films F(T) The kinetic parameter of Mo equation
also confirmed that in situ formed TLCP fibrils could m Ozawa exponent
influence the molecular chain of PP easier to crystallize, n Avrami exponent
and hence resulted in the faster crystallization rate. The t Time
nucleation activity value of composite indicated that TLCP t1/2 Half-time of crystallization
fibrils acted as effective nucleating agents. From TG results Tc Crystallization temperature
and the higher decomposition activation energy, the ther- To The onset crystallization temperatures
mal stability of the composite can be improved by the T? The end crystallization temperature
presence of in situ-formed TLCP fibrils. Tmax The maximum decomposition temperature
Tonset The onset decomposition temperature
Keywords Liquid crystalline polymer  PP  Composites  Xt Relative crystallinity
Crystallization  Kinetics  Thermal stability / Cooling rate
u Nucleation activity
h T - Tmax

S. Saengsuwan (&)  P. Tongkasee  T. Sudyoadsuk 

V. Promarak  T. Keawin  S. Jungsuttiwong Introduction
Center for Organic Electronics and Polymers, Department
of Chemistry and Center for Innovation in Chemistry,
Since the last two decades, thermotropic liquid crystalline
Faculty of Science, Ubon Ratchathani University,
Warinchamrap, Ubon Ratchathani 34190, Thailand polymers (TLCPs) have gained much research attention in
e-mail: scsayasa@ubu.ac.th both academic and industrial fields, due to its various

123
1018
advantages such as superior strength/modulus, low melt
viscosity, low gas permeability, and high chemical/thermal
resistances [1–3]. Therefore, TLCPs have been used to
blend with a variety of thermoplastics (TPs) to obtain the
composite-like materials with a strongly mechanical rein-
forcement of the polymer matrix [1–6]. However, most
TLCP/TPs blends exhibited a two-phase morphology. As
in the molten state, the dispersed TLCP droplets can be
elongated under a sufficient shear or extensional forces and
after rapid solidification, a TLCP fibrillar morphology is
formed producing a so-called in situ composite [7] with
significantly enhanced mechanical properties in the fiber
orientation direction. Moreover, addition of TLCP to a TP
also resulted in a remarkable reduction of the melt viscosity
of the blend, and thus acted as a processing aid with sub-
sequent reduction of wear in processing equipments [4, 6,
8]. Nevertheless, the mechanical properties of the resulting
in situ composites are controlled by their morphology,
which in turn depends on the rheological properties of the
blend, blend composition, interfacial adhesion, and pro-
cessing conditions [9–11]. Thus, by controlling the mor-
phology, the mechanical performance of in situ polymer
composites can be improved. Various fabrication tech-
niques, i.e., fiber spinning, injection molding, and sheet
extrusion, have been used so far to generate the in situ
composites, sheets and films of composites are typically
done by sheet extrusion. The advantages of film fabrication
over other techniques as there are no skin–core effects and
no weld-line formation in the sample. To avoid such
effects, we thus prepared the TLCP/PP in situ composite
film by the sheet extrusion technique.
Polypropylene (PP) is one of the largest used polyolefin in
plastics industry due to its several excellent properties cou-
pled with ease processing and low price. Also, PP is used in
several applications, i.e., packaging, fibers, film, pipes,
transportation, and electrical/electronic applications, etc. The
application ranges of PP can be expanded by addition of
nanoparticles/clays into PP matrix to fabricate the nano-
composite materials [12–14]. In addition, PP can be modified
by blending with TPs [15–17] and TLCPs [5–7, 10, 11].
Despite the fact that various kinds of TLCPs, such as Vectra
A, Vectra B, and Rodrun LC3000 have been used to blend
with PP, only few works reported on the composite system
comprising of PP and Rodrun LC5000. Bualek-Limchroen
et al. [6, 18] have studied the properties of Rodrun LC5000/
PP in situ composite in the forms of as-spun/drawn mono-
filaments and extrusion thin film. They concluded that the
incorporation of Rodrun LC5000 into PP remarkably
improve processability and significantly enhance both mod-
ulus and tensile properties in machine direction of the in situ
composites. However, they did not report on the crystalliza-
tion kinetics and thermal stability of this composite system.
123
S. Saengsuwan et al.
It is well known that the mechanical properties of the
resulting TLCP/TPs in situ composite systems are strongly
dependent on morphology developed, blend composition
and the extent of crystallization, which in turn depends on
the rheological properties, processing conditions and
crystallization behavior of the blend system [1–3, 8–10].
In order to determine the effect of the complex thermal
conditions during processing and to achieve the desired
morphology and properties of the composites, it is
important to study the crystallization kinetics during non-
isothermal conditions and its relationship to the final
properties. Practically, this is because the most industrial
processing techniques generally proceed under dynamic
non-isothermal conditions. Although, several authors have
studied the crystallization kinetics of TLCP/TP blends
[19–26], there are some conflicting results in the effect of
TLCPs on the crystallinity of crystalline polymers. In
some reports, TLCPs acted as nucleating agents for the
spherulites during crystallization process of poly(pheny-
lene sulfide), poly(butylene terephthalate) (PBT) and
poly(ethylene 2,6-napthalate) [19–22]. However, other
works suggested that the crystallization rate of poly(aryl
ether ether ketone) and PBT tended to be decreased
[23, 24]. Moreover, few works have studied on crystalli-
zation kinetics of the TLCP/PP blends. Torre et al. [25],
for instance, studied the isothermal crystallization of PP/
Vectra A950 blend and concluded that Vectra domains
acted as sites for the nucleation of PP, and the crystalli-
zation rate was enhanced with Vectra contents. While
Tjong et al. [26] reported that TLCP phase does not act as
nucleating sites for PP spherulites under isothermal crys-
tallization, but TLCP domain leads to slightly increase in
the crystallization rate of Vectra A950 blended with PP
and maleic anhydride grafted PP.
Many kinetic models such as Avrami, Ozawa, and Mo
methods have been used to describe the crystallization
behavior of the PP phase and its blend systems. However, in
each a particular system, the suitable models for describing
the crystallization behaviors is varied [12–14, 25, 26]. Also,
there is little information on the crystallization kinetics and
thermal stability of PP in situ reinforced by TLCPs micro-
fibrils, especially in the system of Rodrun LC5000/PP fab-
ricated as an extruded thin film, according to author’s
knowledge. Thus, in this work, we are interested to investi-
gate the non-isothermal crystallization kinetics and thermal
stability of an extruded thin film of PP in situ reinforced by
TLCP (Rodrun LC5000) using differential scanning calo-
rimetry (DSC) and thermogravimetry (TG), respectively.
The models of modified Avrami, Ozawa, and Mo were
employed to achieve the relevant kinetic parameters. The
crystallization activation energies based on Kissinger’s
method and nucleation activity were also calculated. Finally,
Non-Isothermal crystallization kinetics and thermal stability of composite films 1019

the thermal stability and decomposition activation energy of Results and discussion
TLCP/PP in situ composites were also investigated.
Non-isothermal crystallization behavior

Experimental Crystallization exotherms at different cooling rates of neat

PP and 10 wt%TLCP/PP films are presented in Fig. 1. As
Materials expected, crystallization temperature (Tc) shifts to lower
temperature with increasing cooling rate for both samples,
PP, PRO-FAX 6631, with a melt flow index of 2 g per due to a larger supercooling at higher cooling rates (see
10 min, kindly provided by HMC Co., Thailand, was used Table 1). For each cooling rate, Tc and crystallization
as a matrix phase. The in situ reinforcing phase was TLCP exotherm broadness of the composite films are higher and
(Rodrun LC5000), a copolyester of 80% mol p-hydroxy narrower, respectively, than those of neat PP film. These
benzoic acid (HBA)/20% mol polyethylene terephthalate results imply that the crystallization process of composite
(PET), purchased from Unitika Co., Japan. The melting film is shorter than that of neat PP film, and it also suggests
temperature and a density of TLCP are 280 °C and that the in situ formed TLCP fibrils act as nucleating sites
1.41 g cm-3, respectively. All materials were dried in a for PP crystallization.
vacuum oven at 80 °C for 10 h before use. Relative crystallinity (Xt) as a function of crystallization
temperature (T) and time (t) can be acquired from the
Blending and fabrication of in situ composite films crystallization exotherms of samples as follows:
ZT , ZT1
The composite films were prepared by using a two-step
Xt ¼ ðdH=dT ÞdT ðdH=dT ÞdT ð1Þ
method. A detailed description of the process was pre-
T0 T0
sented elsewhere [6]. Briefly, PP pellets were first melt-
blended with 10 wt% of TLCP in a twin-screw extruder
and then were fabricated as a cast thin film through a mini-
extruder. The film with a high draw ratio of 30 (a die gap to –5 °C min–1
a
film thickness), corresponding to the film thickness of –10 °C min–1
about 22 lm, was prepared and used throughout this work. –15 °C min–1
–20 °C min–1
Heat flow exo >

Non-isothermal crystallization kinetics

The non-isothermal crystallization of 10 wt%TLCP/PP and

neat PP films was studied by DSC, Metller Toledo, 823e.
All DSC measurements were carried out in nitrogen
atmosphere. Samples cut into small pieces of about 3–4 mg
were used. The samples were initially melted at 200 °C for
100 105 110 115 120 125 130
5 min to remove their thermal history. Then the samples
Temperature/°C
were cooled from 200 to 30 °C at four different cooling
rates of 5, 10, 15, and 20 °C min-1, respectively. The
experimental data were then recorded and analyzed using a b
package software program ‘‘Stare 9.0’’.
Heat flow exo >

Thermal stability

The thermal stability of the 10 wt%TLCP/PP and neat PP

films were performed by a thermogravimetric analyzer
(TG), Rigaku TG8120. Film samples cut into small pieces
of about 3–4 mg were heated at a scanning rate of
10 °C min-1 from 30 to 800 °C under nitrogen atmo-
100 105 110 115 120 125 130
spheres. The onset decomposition temperatures (Tonset), the
Temperature/°C
maximum thermal decomposition temperatures (Tmax)
were reported. Finally, the decomposition activation Fig. 1 DSC thermograms of a neat PP and b 10 wt%TLCP/PP films
energy (DE) of samples were evaluated. during non-isothermal crystallization at different cooling rates

123
1020 S. Saengsuwan et al.

Table 1 Non-isothermal crystallization kinetic parameters for PP and 10 wt%TLCP/PP films

Samples //°C min-1 Tc/°C t1/2/min 1/t1/2/min-1 n k kc R2

Neat PP 5 119.5 2.81 0.356 5.1 0.003 0.313 0.9910

10 116.7 1.43 0.669 4.4 0.138 0.820 0.9955
15 112.5 1.06 0.990 4.5 0.625 0.969 0.9987
20 110.5 0.82 1.219 5.0 1.553 1.022 0.9982
10 wt%TLCP/PP 5 121.4 1.71 0.585 4.8 0.052 0.554 0.9975
10 117.4 1.15 0.869 5.7 0.287 0.883 0.9966
15 115.6 0.98 1.020 5.8 2.132 1.052 0.9975
20 112.5 0.72 1.389 5.8 4.007 1.072 0.9983

where To and T? represent the onset and end crystallization
temperatures, respectively. During non-isothermal crys-
tallization process, the relationship between crystallization
time (t) and temperature (T) is given as follows:
t ¼ ðT0  TÞ=/
where t is the crystallization time and / is cooling rate. The
plots of Xt versus t, for both samples at various cooling rates
are shown in Fig. 2. It is seen that all curves show a similar
sigmoidal shape and the upper part of all curves in the plot is
also found to be level off due to the spherulites
100 a 1/t1/2 values of 10 wt%TLCP/PP films are higher than those
80
60
Xt /%
impingement. With increasing cooling rates, the sigmoidal
shapes are shifted to lower temperature of shorter time for
completing the crystallization. From Fig 2, half-time of
crystallization, t1/2, can be obtained when the Xt are equal to
ð2Þ 50%, and the parameters are listed in Table 1. The value of
t1/2 directly indicate the crystallization rate and the reci-
procal of t1/2 value (time-1) is usually used to compare the
crystallization rates of different systems, i.e., long t1/2 or
less 1/t1/2 indicates the slow crystallization [27]. As seen in
Table 1, t1/2 values of both samples decrease with increas-
ing cooling rates, indicating a progressively faster crystal-
lization rates as the cooling rate increases. Furthermore,
of the neat PP film at each cooling rates, indicating the
higher overall crystallization rate of 10 wt%TLCP/PP film
than neat PP one. Therefore, according to t1/2 and 1/t1/2
values, it could be concluded that the TLCP fibrils act as a

40 nucleating agent and accelerate the overall crystallization

process of PP phase.
–5 °C min–1
20 –10 °C min–1
–15 °C min–1
0 –20 °C min–1
Non-isothermal crystallization kinetic analysis

0 1 2 3 4 5
Analysis based on the Avrami theory modified by Jeziorny
t /min

Avrami theory [28] is generally used for analyzing the

100 b
primary stage of isothermal crystallization kinetics. This
80 approach ignores the effect of cooling rate and thermal
gradients within the sample. According to the model, the
60 relative crystallinity (Xt) develops with crystallization time
Xt /%

(t) as follows:
40
Xt ¼ 1  expðktn Þ ð3Þ
20
ln½ lnð1  Xt Þ ¼ ln k þ n ln t ð4Þ
0
where n is Avrami exponent depending on crystal growth
0 1 2 3 4 5 mechanism, and k is the rate constant involving both
t /min nucleation and growth rate parameters. Both n and k can be
obtained from the slope and intercept of the curves,
Fig. 2 Relative crystallinity versus time for non-isothermal crystal-
lization of a neat PP and b 10 wt%TLCP/PP films at different cooling respectively. In order to make this model applicable to the
rates non-isothermal crystallization process, Jeziorny [29] thus

123
Non-Isothermal crystallization kinetics and thermal stability of composite films 1021

3 non-isothermal crystallization of the composite corresponds

a to solid sheaf-like growth with heterogeneous nucleation,
2
and the TLCP fibrils acted as sites for nucleation in PP
1 matrix [14, 30]. The values of k and kc of both samples
ln(ln(1 – Xt))

0 slightly increase with increasing cooling rates, since both

parameters are the measurement of crystallization rate that
–1 gets faster with increasing cooling rate. Furthermore, at a
–2 –5 °C min–1 given cooling rates, the kc values of composite is higher
–10 °C min–1 than those of neat PP film, demonstrating that the crystal-
–3 –15 °C min–1
–20 °C min–1
lization rates of composite films are higher than neat PP one
–4 corresponding to the t1/2 and 1/t1/2 values as discussed
–2 –1 0 1 2 earlier.
ln t
3
Analysis based on the Ozawa method
b
2
The mostly used kinetic model for analyzing the non-iso-
1
thermal crystallization process of polymers is Ozawa
ln(–ln(1 – Xt))

0 method [31]. This method extended the Avrami equation

–1
–2
–3
–4
–2 –1 0 1
ln t
Fig. 3 Avrami plots of ln(-ln(1 - Xt)) versus ln t for non-isother-
mal crystallization of a neat PP and b 10 wt%TLCP/PP films
considered to correct the crystallization rate constant by
introducing the cooling rate (/) because temperature
changed at a given cooling rate affects the rate of both
nucleation and spherulite growth which are temperature
dependent parameter. The modified equation is expressed
as follows:
ln kc ¼ ln k=/
where kc is the kinetic crystallization rate constant. Figure 3
presents Avrami plots of the neat PP and 10 wt%TLCP/PP
films at various cooling rates. Each curve in Fig. 3 exhibits
good linear relationship except a secondary crystallization
at the latter crystallization state, normally considering to be
due to the slow crystallization and further perfection of
crystals. However, the modified Avrami equation can be
used to describe a large range of relative crystallinity. Thus,
the linear line in the middle portion of the curves in Fig. 3 is
adopted to determine Avrami exponent (n) and the corre-
sponding rate parameters as listed in Table 1. The average
values of n for neat PP and 10 wt%TLCP/PP films are 4.8
and 5.5, respectively. The Avrami exponent n [ 4 indicates
a more complicated nucleation type and spherulite growth
form. Also, the average exponent n for 10 wt%TLCP/PP
was larger than that for neat PP film indicating that the
by assuming that the crystallization process is composed of
small isothermal crystallization steps (i.e., replacing the
time variable with cooling rate term) [32] and developed a
formula as follows:
Xt ¼ 1  expðKðTÞ=/m Þ ð6Þ
2
ln½ lnð1  Xt Þ ¼ ln KðTÞ  m ln / ð7Þ
where K(T) is the function of cooling rate related to overall
crystallization rate indicating how fast crystallization pro-
ceeds, which takes into account the geometry and change
in nucleation density and growth rate, and m is the Ozawa
exponent (similar to n but in different form) depending
on the dimension of crystal growth. By plotting
ln[-ln(1 - Xt)] versus ln / at a given temperature, a series
of straight line could be obtained if the Ozawa method was
valid where the crystallization kinetic parameters K(T) and
m can be derived from the intercept and slope, respectively.
ð5Þ
The results of the Ozawa analysis for neat PP and com-
posite films are presented in Fig. 4. It is clearly seen that
most curves in the plots did not exhibit a linear relation-
ship, especially at low temperature (114 °C). Moreover,
there is a variation of slope as a function of temperature
suggesting that m is not a constant during the process of
non-isothermal crystallization. This observation can be
explained as the crystallization processes at a given tem-
perature with different cooling rates are at different stages,
i.e., at higher cooling rate, the crystallization process is at
an earlier stage and vice versa [12]. In addition, the Ozawa
method ignored the secondary crystallization and the
dependence of the lamellar thickness on crystallization
temperature [32]. In general, a large portion of crystallinity
is attributed to the secondary crystallization, especially for
semi-crystalline polymers such as isotactic PP. From these
information, it could be stated that m depends not only on

123
1022 S. Saengsuwan et al.

2
a 3.2 a
0
2.8
ln(–ln(1 – X t))

–2
2.4

ln φ
–4 114 20%
2.0
116 40%
118 60%
–6 120 1.6 80%
122
124
–8
–0.8 –0.4 0.0 0.4 0.8 1.2 1.6
1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2
ln t
ln φ

2 3.2 b
b
0 2.8
ln(–ln(1 – Xt ))

ln φ
–2 2.4

–4 114 2.0
116
118 1.6
–6 120
122
124 –0.8 –0.4 0.0 0.4 0.8 1.2 1.6
–8
1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 ln t
ln φ
Fig. 5 Plots of ln / versus ln t from the Mo method for non-
Fig. 4 Ozawa plots of ln(-ln(1 - Xt)) versus ln / for non-isother- isothermal crystallization of a neat PP and b 10 wt%TLCP/PP films
mal crystallization of a neat PP and b 10 wt%TLCP/PP films
The smaller value of F(T), the higher crystallization rate or
the dimension of crystal growth, but also on other param- vice versa. And the importance of this method, the cooling
eters such as time-dependent nucleation, variant growth rate was correlated to temperature and time of the non-
rate constant as well as a combination of homogeneous and isothermal crystallization process. Therefore, F(T) has both
heterogeneous nucleation [21, 30, 32, 33]. As a conse- definite physical and practical meaning. According to Eq. 8,
quence, the Ozawa analysis is not adequately applicable for at a given Xt, the plot of ln / versus ln t should yield a
studying the non-isothermal crystallization process of both straight line with ln F(T) and a as the intercept and slope,
neat PP and 10 wt%TLCP/PP films. respectively, if Mo analysis is valid. As seen in Fig. 5,
plotting of ln / against ln t for neat PP and composite films
Analysis based on the Mo theory shows a good linearity at a given Xt, verifying that the Mo
method is applicable to the both systems. The values of a
In order to better describe the overall process of the non- and F(T) are evaluated and summarized in Table 2. It is
isothermal crystallization process of neat PP and 10 wt% seen that the value of a for neat PP and composite samples
TLCP/PP films, Mo method has been applied. Liu et al. [34] varies from 1.09 to 1.18 and 1.12 to 1.25, respectively. In
proposed an alternative kinetic equation by combining the addition, the values of F(T) systematically increase with
Avrami (Eq. 4) and Ozawa (Eq. 7) equations, which is given increasing the relative crystallinity, suggesting that at a unit
by: crystallization time, a higher cooling rate is required to
obtain a higher degree of crystallinity. The F(T) values of
ln / ¼ ln FðTÞ  a ln t ð8Þ
neat PP sample are found to vary from 12.06 to 19.49, while
1/m
where F(T) = [K(T)/k] and a = n/m, the ratio of the those of composite sample are in the range of 11.59–17.63,
Avrami exponent n to the Ozawa exponent m. The kinetic as the Xt is increased. Moreover, the F(T) values of com-
parameter of Mo F(T) refers to the value of cooling rate posite sample at each given crystallinity are found to be
chosen at a unit crystallization time when system amounted smaller than those of neat PP, i.e., to reach the same Xt, the
to a certain degree of crystallinity, relating to the difficulty 10 wt%TLCP/PP sample needs smaller cooling rates
of the crystallization process for that particular material. because it crystallizes at a faster rate than the neat PP one.

123
Non-Isothermal crystallization kinetics and thermal stability of composite films 1023

Table 2 Crystallization kinetic parameters obtained from Mo found to be 269 and 210 kJ mol-1, respectively. The
method and crystallization activation energy of PP and 10 wt%TLCP/ DE value of the composite sample strongly decreases com-
PP films calculated by Kissinger method pared to that of neat PP one. This implies that TLCP fibrils
Samples Xt a F(T) R2 -DE/kJ mol-1 influence the PP chains to crystallize easier and accelerate
the rate of crystallization during the non-isothermal crys-
Neat PP 20 1.08 12.06 0.9922 269
tallization process [14]. This result is also in good accor-
40 1.11 14.44 0.9948
dance with the higher crystallization rate of 10 wt%TLCP/
60 1.14 16.78 0.9950
PP, obtained from the modified Avrami and Mo method.
80 1.18 19.49 0.9967
10 wt%TLCP/PP 20 1.12 11.59 0.9975 210
Nucleation activity
40 1.16 13.46 0.9963
60 1.19 15.49 0.9942
A simple approach for estimating the nucleation activity of
80 1.25 17.63 0.9943
foreign substrates in polymer melt was suggested by
Dobreva et al. [36, 37]. Nucleation activity (u) is a factor by
which the work of three-dimensional nucleation decreases
This result suggests that TLCP fibers act as a heteroge- with the incorporating of a foreign agent. If the foreign
neously nucleating agent and accelerate the crystallization agent is extremely active, u approximates 0 and reaches 1
of PP. for inert agents. The u is calculated from the ratio:
u ¼ B =B ð10Þ
Activation energy of crystallization by Kissinger method
where B is a parameter calculating from the following
In order to evaluate the effective energy barrier for non- relation:
isothermal crystallization process, the Kissinger method B ¼ xr3 Vm2 =3nkTm DS2m ð11Þ
[35] has been employed. From this method, the activation
energy (DE) for transporting of the macromolecular seg- where x is geometric factor, r is the specific energy, Vm is
ments to the growing crystal surface can be determined. the molar volume of the crystallizing substance, k is the
The equation is written as follows: Boltzmann constant, and DSm is the entropy of melting. In
addition, B can be experimentally examined from the slope
d½lnð/=Tc2 Þ=dð1=Tc Þ ¼ ½DE=R ð9Þ
of Eq. 12 obtained by plotting ln / and 1=DTc2 :
where Tc, /, DE and R are the crystallization temperature,
ln / ¼ A  ðB=DTc2 Þ ð12Þ
cooling rate, the crystallization activation energy and the gas
constant, respectively. From the plot of lnð/=Tc2 Þ versus where A is a constant, and DTc is the degree of super-
(1/Tc), as shown in Fig. 6, the crystallization activation cooling, i.e., DTc = Tm - Tc. This equation holds for
energy (DE) can be calculated from the slope as listed in homogeneous nucleation from a melt near the melting
Table 2. The DE values of neat PP and composite films are temperature. To apply this to a heterogeneous nucleating
agent, Eq. 12 is transformed to the following:
ln / ¼ A  ðB =DTc2 Þ ð13Þ
–8.8
Figure 7 presents the relationship between of ln / and
–9.2
1=DTc2 for the neat PP and composite samples. As can be
seen, a series of straight lines are obtained in both samples
ln(φ /Tc2 )

(R2 [ 0.998). From the slope, the values of B and B* are

–9.6
6.1 9 103 and 5.1 9 103 K2, respectively. Then by
computing from Eq. 10, the nucleation activity (u) of the
–10.0 10 wt%TLCP/PP sample was 0.83. This indicates the
Neat PP incorporation of in situ formed TLCP fibrils acting
10wt%TLCP/PP effectively as a heterogeneous nucleation agent in the PP
–10.4
matrix.
2.52 × 10 –3 2.54 × 10 –3 2.56 × 10 –3 2.58 × 10 –3 2.60 × 10 –3

T c–1/K –1 Thermal stability of 10 wt%TLCP/PP composite film

Fig. 6 Kissinger plots of lnð/=Tc2 Þ versus
1/Tc for calculating the
non-isothermal crystallization activation energies of neat PP and Thermogravimetric (TG) and corresponding differential
10 wt%TLCP/PP films thermogravimetric (DTG) thermograms of the neat PP and

123
1024 S. Saengsuwan et al.

3.2 Table 3 Parameters evaluated from TG and DTG thermograms of

neat PP film, 10 wt%TLCP/PP film and TLCP sheets
2.8 Samples Ti/°C Tmax/°C DE/kJ mol-1

2.4 Neat PP 362 402 159

10 wt%TLCP/PP 373 418 183
ln φ

2.0 TLCP sheeta 417 450 221

a
Evaluated from the first thermal decomposition stage only
1.6 Neat PP
10wt%TLCP/PP
of the two pathways of mechanism which occurred simul-
1.2 taneously [38]. On the contrary, the TLCP (Rodrun LC5000)
4.0 × 10–4 5.0 × 10 –4 6.0 × 10–4 7.0 × 10 –4
sheet exhibited three-step decompositions at temperature of
ΔT c–2 /K –2 410–730 °C (see Fig. 8a) with three maxima rate peaks at
450, 510, and 630 °C (see Fig. 8b), respectively. The first
Fig. 7 Relationship between ln / and 1=DTc2 for calculating the
nucleation activity of neat PP and 10 wt%TLCP/PP films two-steps decomposition corresponds to the decomposition
of PET component and the final step corresponds to the
decomposition of HBA component. For the 10 wt%TLCP/
0 a PP films, a single-step weight loss was observed with its
–20 Neat PP corresponding maximum rate peak at 418 °C. The onset
10wt%TLCP/PP (Tonset) and maximum (Tmax) decomposition temperatures of
TLCP sheet
Mass loss/%

–40 the samples are summarized in Table 3. It is seen that both

Tonset and Tmax of the composite film are higher than those of
–60 the neat PP film, indicating that incorporation of TLCP phase
leads to the improvement of thermal stability of PP matrix.
–80 These data agree well with the TG results of extruded stands
of TLCP/PP blends reported by Saikrasun and Saengsuwan
–100
[39].
200 300 400 500 600 700 800 The activation energy (DE) for thermal degradation of
Temperature/°C the samples was evaluated from the TG curves using the
method of Horowitz and Metzger [40] as follows:
b  2
0 ln½lnðW0 =WT Þ ¼ DEh RTmax ð14Þ
where W0 and WT are the initial and residual weight of the
DTG/%min –1

–3 polymer at temperature T, and h is T - Tmax. The activa-

tion energies were obtained from the slope of the plot of
–6 ln(ln(W0/WT)) versus h (see Table 3), as presented in Fig. 9.

–9 Neat PP
0
10wt%TLCP/PP
TLCP sheet
–12 –1
200 300 400 500 600 700 800
ln[ln(W 0/WT )]

Temperature/°C
–2
Fig. 8 a TG and b DTG thermograms of neat PP film, 10 wt%TLCP/
PP film and TLCP sheet measured at a scanning rate of 10 °C min-1
under N2 atmosphere –3
PP
10wt%TLCP/PP
–4 TLCP
10 wt%TLCP/PP films measured at a heating rate of
10 °C min-1 in N2 are presented in Figs. 8a and b, respec- –50 –40 –30 –20 –10 0
tively. Clearly, the neat PP film occurred in only single-step θ /K
mass loss at temperature of 300–450 °C (see Fig. 8a) with
Fig. 9 Plot of ln[ln(W0/WT)] versus h for calculating the decompo-
one maximum rate peak at 402 °C (see Fig. 8b), corre- sition activation energy of the neat PP film, 10 wt%TLCP/PP film and
sponding to the decomposition of PP backbone comprising TLCP sheet

123
Non-Isothermal crystallization kinetics and thermal stability of composite films
The decomposition activation energies of neat PP,
10 wt%TLCP/PP and TLCP are 159, 183 and 221 kJ mol-1,
respectively. The DE of composite sample is remarkable
higher than that of neat PP film, corresponding to their Tonset
and Tmax. This result suggests that TLCP fibrils in situ
formed in PP matrix during processing can significantly
improve the thermal stability of PP blend.
Conclusions
The study on non-isothermal crystallization kinetics and
thermal stability of the composite influenced by in situ
formed TLCP fibrils using DSC and TGA, respectively,
showed that the Tc and t1/2 of composite films were higher
and lower than those of neat PP films at each cooling rate,
respectively. This suggested that the overall crystallization
rate of composite film was faster than that of neat PP one.
Also, it was implied that TLCP fibrils acted as heteroge-
neous nucleating sites in PP matrix. To analyze the non-
isothermal crystallization kinetics of samples, three kinetic
models; modified Avrami, Ozawa, and Mo methods, were
employed. The studies demonstrated that Mo method
successfully described the non-isothermal crystallization
process in both systems. The F(T) values of the composite
film were smaller than that of neat PP film, suggesting the
faster crystallization rate of PP in the composite due to the
nucleating effect of in situ generated TLCP fibers in PP
phases. The crystallization activation energy based on
Kissinger method of the composite was found to be much
smaller than that of PP film, indicating the easier move-
ment of PP molecular chains in the TLCP/PP systems
which subsequently resulted in the faster crystallization
rate of PP. In addition, the calculated nucleation activity of
composite agreed very well with the reduction of t1/2,
F(T) and crystallization activation energy in the composite
sample.
Finally, the thermal stability of the composite film was
also investigated in N2 atmosphere. The results revealed
that both Tonset and Tmax of the composite were shifted to
higher temperatures. Also, the decomposition activation
energy of the composite was higher than that of PP. These
results suggested that in situ forming of TLCP fibrils in PP
matrix significantly improved the thermal stability of
composite which could extend the application ranges of
TLCP/PP composites.
Acknowledgements This study was funded by a grant from the
Thailand Research Fund (MRG4780032). Partial financial supports
from the Center for Innovation in Chemistry (PERCH-CIC), Com-
mission on Higher Education, Ministry of Education and Ubon
Ratchathani University are also acknowledged. The SS author also
grateful thanks to Prof. Sauvarop Bualek-Limcharoen for providing
TLCP and giving the useful discussion.
1025
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